The Grignard Reaction – Unraveling a Chemical Puzzle
Raphael Mathias PeltzerDepartment of Chemistry and Hylleraas Centre for Quantum Molecular Sciences, University of Oslo, P.O. Box 1033 Blindern, Oslo 0315, NorwayJürgen GaußDepartment Chemie, Johannes Gutenberg-Universität Mainz, Duesbergweg 10-14, Mainz 55128, GermanyOdile EisensteinDepartment of Chemistry and Hylleraas Centre for Quantum Molecular Sciences, University of Oslo, P.O. Box 1033 Blindern, Oslo 0315, NorwayMichele CascellaDepartment of Chemistry and Hylleraas Centre for Quantum Molecular Sciences, University of Oslo, P.O. Box 1033 Blindern, Oslo 0315, Norway
2020en
ABI
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bond, cannot occur unless a substrate with a low-lying π*(CO) orbital coordinates the Mg center. This rationalizes why a radical mechanism is detected only in the presence of substrates with a low reduction potential. This feature, in turn, does not necessarily favor the nucleophilic addition, as shown for the reaction with fluorenone. The solvent needs to be considered as a reactant for both the nucleophilic and the radical reactions, and its dynamics is essential for representing the energy profile. The similar reactivity of several species in fast equilibrium implies that the reaction does not occur via a single process but by an ensemble of parallel reactions.
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